CN106904959A - Y3+、Ga3+Compound donor doping ZnO voltage-sensitive ceramics and preparation method - Google Patents

Y3+、Ga3+Compound donor doping ZnO voltage-sensitive ceramics and preparation method Download PDF

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CN106904959A
CN106904959A CN201710239613.4A CN201710239613A CN106904959A CN 106904959 A CN106904959 A CN 106904959A CN 201710239613 A CN201710239613 A CN 201710239613A CN 106904959 A CN106904959 A CN 106904959A
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庞驰
张宁
方超
周芳
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Guiyang Hi Tec Yige Electronic Co ltd
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Guizhou University
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Abstract

The invention discloses a kind of Y3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping and preparation method thereof, include base-material and doping is expected, the base-material includes ZnO by weight：87 95 parts, Bi2O3：2.0 4.0 parts, MnO2：0.4 0.7 parts, Sb2O3：1.5 3.5 parts, Co2O3：0.5 1.5 parts, Cr2O3：0.2 1.0 parts, seed crystal doping material：15 parts；The seed crystal doping material is ZnO, Ga2O3And Y2O3, its mass fraction ratio is ZnO：Ga2O3：Y2O3=90 95：0.1‑5：0.1‑5.Y of the present invention3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping have can reduce ZnO grain resistance rates, the characteristics of can control ZnO distortions of lattice again, be finally reached the characteristics of ZnO varistor residual voltage is low, aging life-span is long, pulse current tolerance is strong.

Description

Y3+、Ga3+Compound donor doping ZnO voltage-sensitive ceramics and preparation method
Technical field
The present invention relates to a kind of ZnO voltage-sensitive ceramics and preparation method thereof, particularly one kind is without Al3+The Y of doping3+、Ga3+It is multiple Close donor doping ZnO voltage-sensitive ceramics and preparation method thereof.
Background technology
ZnO varistor is, with ZnO as primary raw material, to add a small amount of Bi2O3、Co3O4、MnO2、Sb2O3、Cr2O3Deng raw material, It is prepared from using ceramic sintering process.Piezo-resistance has the advantages that good non-linear and big through-current capability, and it is used as thunder Electric surge protector component is widely used in electronic circuit and power system.It is swift and violent with microelectronics information technology Development, it is miniaturization to component, integrated so that modular requirement is more and more urgent.The electronic component sensitivity of miniaturization High, anti overvoltage level is low, and this improves electronic equipment to the demand of lightning protection, it is necessary to ZnO varistor can have lower Residual voltage level of protection.
When lightning current invades equipment, the ZnO crystal boundaries conducting of ZnO varistor, its performance mainly has ZnO grain resistances to determine It is fixed.Reduce the residual voltage of ZnO varistor, it is necessary to reduce the resistivity of ZnO varistor.
Existing method one：ZnO varistor original is added to as donor ion using Al ions mostly in the industrial production In material.0.005mol%Al ions normally only be with the addition of as donor ion, therefore cause the reduction of ZnO varistor rate not Substantially.But if adding substantial amounts of Al ions as donor ion, Spinel and richness can be entered due to addition Al ions again In Bi phases, interface state density is caused to decline the reduction with barrier height.So that the leakage current of ZnO varistor is increased dramatically, Nonlinear factor declines.
Existing method two：In order to by donor ion Al Effective Dopings to ZnO crystal grain, some enterprises improve production work Skill, first by ZnO and Al (NO3)3·9H2O mixes, and in 1200 DEG C~1300 DEG C temperature lower calcinations, seed crystal is made, then again by seed Crystalline substance is added in the dispensing of ZnO varistor, and piezo-resistance is prepared using ceramic sintering process, and do so can avoid Al ions Into in Spinel and richness Bi phases, interface state density is caused to decline the reduction with barrier height.Above method can reach drop The purpose of low residual voltage, while also obtaining certain effect.In order to be able to reduce ZnO grain resistances, except using seed crystal two above Outside stage production technology, often adulterate substantial amounts of donor ion Al.But because Al ionic radius are only 0.0535nm, and Zn ions Radius is 0.074nm, and both ionic radius differences cause ZnO distortions of lattice serious than larger after forming donor doping, and this must So cause the performance indications such as ZnO varistor aging life-span, pulse current tolerance to decline to a great extent, commercial Application can not be met Demand.
The content of the invention
It is an object of the present invention to develop one kind without Al3+The ZnO voltage-sensitive ceramics formula and preparation method of doping, the present invention Y3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping have can reduce ZnO grain resistance rates, and ZnO lattices can be controlled again The characteristics of distortion, it is finally reached the characteristics of ZnO varistor residual voltage is low, aging life-span is long, pulse current tolerance is strong.
Technical scheme：A kind of Y3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping, include base-material Expect with doping, the base-material includes ZnO by weight：87-95 parts, Bi2O3：2.0-4.0 parts, MnO2：0.4-0.7 parts, Sb2O3：1.5-3.5 parts, Co2O3：0.5-1.5 parts, Cr2O3：0.2-1.0 parts, seed crystal doping material：1-5 parts；The seed crystal doping material It is ZnO, Ga2O3And Y2O3, its mass fraction ratio is ZnO：Ga2O3：Y2O3=90-95：0.1-5：0.1-5.
Foregoing Y3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping, the base-material is included by weight ZnO：89-92 parts, Bi2O3：2.5-3.5 parts, MnO2：0.5-0.6 parts, Sb2O3：2-3 parts, Co2O3：0.8-1.2 parts, Cr2O3： 0.3-0.8 parts, seed crystal doping material：2-4 parts；The seed crystal doping material is ZnO, Ga2O3And Y2O3, its mass fraction ratio is ZnO： Ga2O3：Y2O3=92-94：1-4：1-3.
Foregoing Y3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping, the base-material is included by weight ZnO：90.5 parts, Bi2O3：3.0 parts, MnO2：0.5 part, Sb2O3：2.5 parts, Co2O3：1 part, Cr2O3：0.5 part, seed crystal doping material 2 Part, the seed crystal doping material mass fraction ratio is ZnO：Ga2O3：Y2O3=94：3：3.
A kind of foregoing Y3+、Ga3+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, comprises the following steps：
(1) seed crystal is prefabricated：By ZnO：Ga2O3：Y2O3Mix in the ratio, Ga2O3And Y2O3Can be in the form of nitrate Add, while adding alcohol or deionized water, ball milling 8-24 hours, form seed crystal suspension, by the drying of seed crystal suspension, obtain seed Brilliant batch；
(2) seed crystal sintering：Sintered 3-6 hours at seed crystal batch obtained in step (1) is put into 1200-1350 DEG C, burnt Normal temperature is slowly dropped to stove after knot, seed crystal sintering feed is made；
(3) seed crystal ball milling：By seed crystal sintering feed ball-milling treatment obtained in step (2), seed crystal average grain diameter is less than 5 μm, system Obtain seed crystal standby；
(4) dispensing, granulation, base：To being proportionally added into ZnO, Bi in seed crystal obtained in step (3)2O3、MnO2、Sb2O3、 Co2O3And Cr2O3Mixing, to deionized water, poly-vinyl alcohol solution, dispersant is added in mixture, ball milling 8-12 hours, obtains Suspension, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate obtained in step (4) is put into electric furnace and is warming up to 400 DEG C and is carried out insulation dumping, dumping Time 4-6 hours, 1200-1350 DEG C is warming up to after dumping and is sintered, sintering time 18-23 hours, be incubated after the completion of sintering 3-6 hours, make its densification into porcelain, be then cooled to normal temperature with stove.
Foregoing Y3+、Ga3+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, in the step (1), Ball-milling Time It is 15-17 hours.
Foregoing Y3+、Ga3+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, is by step in the step (2) (1) seed material obtained in is sintered 4-5 hours at being put into 1270-1280 DEG C.
Foregoing Y3+、Ga3+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, in the step (4), adds poly- second The mass percent of enolate solution is 5%wt, and the ratio for adding poly-vinyl alcohol solution is the addition poly- second of 50g in every kilogram of mixture Enolate solution.
Beneficial effects of the present invention：The present invention by be combined donor doping Ga ions and Y-ion, because Ga ionic radius are 0.062nm, Y-ion radius is 0.09nm, and Zn ionic radius are 0.074nm.The ionic radius of Ga, Y, Zn is more or less the same, easily Adulterated in instead type is formed, and Ga ions, Y-ion instead of Zn ion lattice sites in Pb-Zn deposits structure, Ga ion displacements Doping causes the Lattice Contraction, Y-ion displacement doping to cause lattice dilatation, can be by controlling the doping ratio of Ga ions, Y-ion Carry out precise control ZnO distortions of lattice, donor doping reduces grain resistance rate and reduces ZnO varistor residual voltage, inhibits and let out While growth, the decline of suppression nonlinear factor of leakage current, ZnO varistor aging life-span, pulse current are enhanced again Tolerance, so that the material has performance higher and is more suitable for commercial Application.
This experimental example makes laboratory sample with 3 kinds of different manufacture crafts altogether, and the first is traditional handicraft, and traditional handicraft is not Plus seed crystal doping material；Second is the technique of addition seed crystal, as described in the background art shown in existing method two；The third according to It is prepared by the method for the invention；The pressure sensitive voltage of test sample, leakage current, nominal discharge current, residual voltage, accelerated life, Result is as shown in table 1.
The correction data of table 1
By table 1：Using patented technology of the present invention prepare sample leakage current it is smaller, residual voltage is lower, pulse current Tolerance is stronger, aging life-span is longer, the sample that its electrical property is prepared better than traditional handicraft and existing method two comprehensively.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but is not intended as the foundation to present invention limitation.
Embodiments of the invention
Embodiment 1：A kind of Y3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping, include base-material and doping is expected, The base-material includes ZnO by weight：90.5 parts, Bi2O3：3.0 parts, MnO2：0.5 part, Sb2O3：2.5 parts, Co2O3：1 Part, Cr2O3：0.5 part, 2 parts of seed crystal doping material, the seed crystal doping material mass fraction ratio is ZnO：Ga(NO3)3:Y(NO3)3= 94：3：3.
Embodiment 2：A kind of Y3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping, include base-material and doping is expected, The base-material includes ZnO by weight：87 parts, Bi2O3：2.0 parts, MnO2：0.4 part, Sb2O3：1.5 parts, Co2O3：0.5 Part, Cr2O3：0.2 part, seed crystal doping material：1 part；The seed crystal doping material is ZnO, Ga2O3And Y2O3, its mass fraction ratio is ZnO：Ga2O3：Y2O3=90：0.1：0.1.
Embodiment 3：A kind of Y3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping, include base-material and doping is expected, The base-material includes ZnO by weight：95 parts, Bi2O3：4.0 parts, MnO2：0.7 part, Sb2O3：3.5 parts, Co2O3：1.5 Part, Cr2O3：1.0 parts, seed crystal doping material：5 parts；The seed crystal doping material is ZnO, Ga2O3And Y2O3, its mass fraction ratio is ZnO：Ga2O3：Y2O3=95：5：5.
Embodiment 4：Above-mentioned Y3+、Ga3+The preparation method of ZnO voltage-sensitive ceramics prepared by compound donor doping, step is such as Under：
(1) seed crystal is prefabricated：By ZnO, Ga2O3And Y2O3Mix in the ratio, add deionized water and alcohol, ball milling 16 Hour, seed crystal suspension is formed, by the drying of seed crystal suspension, obtain seed crystal batch；
(2) seed crystal sintering：Sintered 4 hours at seed crystal batch obtained in step (1) is put into 1270 DEG C, with stove after sintering Normal temperature is slowly dropped to, seed crystal sintering feed is made；
(3) seed crystal ball milling：By seed crystal sintering feed ball-milling treatment obtained in step (2), seed crystal average grain diameter is less than 5 μm, system Obtain seed crystal standby；
(4) dispensing, granulation, base：To being proportionally added into ZnO, Bi in seed crystal sintering feed obtained in step (3)2O3、MnO2、 Sb2O3、Co2O3And Cr2O3Mixing, obtains to deionized water, poly-vinyl alcohol solution, dispersant, ball milling 10 hours is added in mixture Suspension, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate obtained in step (4) is put into electric furnace and is warming up to 400 DEG C and is carried out insulation dumping, dumping 5 hours time, 1270 DEG C are warming up to after dumping and are sintered, sintering time 20 hours is incubated 4 hours after the completion of sintering, makes it Then densification is cooled to normal temperature into porcelain with stove.
In above-mentioned steps (4), the mass percent for adding poly-vinyl alcohol solution is 5%wt, adds poly-vinyl alcohol solution Ratio is addition 50g poly-vinyl alcohol solutions in every kilogram of mixture.
Embodiment 5：Above-mentioned Y3+、Ga3+The preparation method of ZnO voltage-sensitive ceramics prepared by compound donor doping, step is such as Under：
(1) seed crystal is prefabricated：By ZnO, Ga (NO3)3With Y (NO3)3Mix in the ratio, add deionized water and alcohol, Ball milling 8 hours, forms seed crystal suspension, by the drying of seed crystal suspension, obtains seed crystal batch；
(2) seed crystal sintering：Sintered 6 hours at seed crystal batch obtained in step (1) is put into 1200 DEG C, with stove after sintering Normal temperature is slowly dropped to, seed crystal sintering feed is made；
(3) seed crystal ball milling：By seed crystal sintering feed ball-milling treatment obtained in step (2), seed crystal average grain diameter is less than 5 μm, system Obtain seed crystal standby；
(4) dispensing, granulation, base：To being proportionally added into ZnO, Bi in seed crystal sintering feed obtained in step (3)2O3、MnO2、 Sb2O3、Co2O3And Cr2O3Mixing, obtains to deionized water, poly-vinyl alcohol solution, dispersant, ball milling 12 hours is added in mixture Suspension, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate obtained in step (4) is put into electric furnace and is warming up to 400 DEG C and is carried out insulation dumping, dumping 4 hours time, 1200 DEG C are warming up to after dumping and are sintered, sintering time 23 hours is incubated 3 hours after the completion of sintering, makes it Then densification is cooled to normal temperature into porcelain with stove.
In above-mentioned steps (4), the mass percent for adding poly-vinyl alcohol solution is 5%wt, adds poly-vinyl alcohol solution Ratio is addition 50g poly-vinyl alcohol solutions in every kilogram of mixture.
Embodiment 6：Above-mentioned Y3+、Ga3+The preparation method of ZnO voltage-sensitive ceramics prepared by compound donor doping, step is such as Under：
(1) seed crystal is prefabricated：By ZnO, Ga2O3And Y2O3Mix in the ratio, add deionized water and alcohol, ball milling 24 Hour, seed crystal suspension is formed, by the drying of seed crystal suspension, obtain seed crystal batch；
(2) seed crystal sintering：Sintered 3 hours at seed crystal batch obtained in step (1) is put into 1350 DEG C, with stove after sintering Normal temperature is slowly dropped to, seed crystal sintering feed is made；
(3) seed crystal ball milling：By seed crystal sintering feed ball-milling treatment obtained in step (2), seed crystal average grain diameter is less than 5 μm, system Obtain seed crystal standby；
(4) dispensing, granulation, base：To being proportionally added into ZnO, Bi in seed crystal sintering feed obtained in step (3)2O3、MnO2、 Sb2O3、Co2O3And Cr2O3Mixing, obtains to deionized water, poly-vinyl alcohol solution, dispersant, ball milling 12 hours is added in mixture Suspension, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate obtained in step (4) is put into electric furnace and is warming up to 400 DEG C and is carried out insulation dumping, dumping 6 hours time, 1350 DEG C are warming up to after dumping and are sintered, sintering time 18 hours is incubated 6 hours after the completion of sintering, makes it Then densification is cooled to normal temperature into porcelain with stove.
In above-mentioned steps (4), the mass percent for adding poly-vinyl alcohol solution is 5%wt, adds poly-vinyl alcohol solution Ratio is addition 50g poly-vinyl alcohol solutions in every kilogram of mixture.

Claims (7)

1. a kind of Y3+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping, it is characterised in that：Include base-material and doping expected, The base-material includes ZnO by weight：87-95 parts, Bi2O3：2.0-4.0 parts, MnO2：0.4-0.7 parts, Sb2O3：1.5- 3.5 parts, Co2O3：0.5-1.5 parts, Cr2O3：0.2-1.0 parts, seed crystal doping material：1-5 parts；Seed crystal doping material is ZnO, Ga2O3And Y2O3, its mass fraction ratio is ZnO：Ga2O3：Y2O3=90-95：0.1-5：0.1-5.
2. Y according to claim 13+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping, it is characterised in that：It is described Base-material includes ZnO by weight：89-92 parts, Bi2O3：2.5-3.5 parts, MnO2：0.5-0.6 parts, Sb2O3：2-3 parts, Co2O3：0.8-1.2 parts, Cr2O3：0.3-0.8 parts, seed crystal doping material：2-4 parts；The seed crystal doping material is ZnO, Ga2O3With Y2O3, its mass fraction ratio is ZnO：Ga2O3：Y2O3=92-94：1-4：1-3.
3. Y according to claim 23+、Ga3+ZnO voltage-sensitive ceramics prepared by compound donor doping, it is characterised in that：It is described Base-material includes ZnO by weight：90.5 parts, Bi2O3：3.0 parts, MnO2：0.5 part, Sb2O3：2.5 parts, Co2O3：1 part, Cr2O3：0.5 part, 2 parts of seed crystal doping material, the seed crystal doping material mass fraction ratio is ZnO：Ga2O3：Y2O3=94：3：3.
4. a kind of Y according to claim any one of 1-33+、Ga3+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, It is characterised in that it includes following steps：
(1) seed crystal is prefabricated：By ZnO：Ga2O3：Y2O3Mix in the ratio, Ga2O3And Y2O3Can be added in the form of nitrate Enter, while adding alcohol or deionized water, ball milling 8-24 hours, form seed crystal suspension, by the drying of seed crystal suspension, obtain seed crystal Batch；
(2) seed crystal sintering：Sintered 3-6 hours at seed crystal batch obtained in step (1) is put into 1200-1350 DEG C, after sintering Normal temperature is slowly dropped to stove, seed crystal sintering feed is made；
(3) seed crystal ball milling：Seed crystal sintering feed ball-milling treatment obtained in step (2), seed crystal average grain diameter are less than 5 μm, seed is obtained It is brilliant standby；
(4) dispensing, granulation, base：To being proportionally added into ZnO, Bi in seed crystal obtained in step (3)2O3、MnO2、Sb2O3、Co2O3 And Cr2O3Mixing, to deionized water, poly-vinyl alcohol solution, dispersant is added in mixture, ball milling 8-12 hours, is suspended Liquid, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate obtained in step (4) is put into electric furnace and is warming up to 400 DEG C and is carried out insulation dumping, dumping time 4-6 hours, 1200-1350 DEG C is warming up to after dumping and is sintered, sintering time 18-23 hours, 3-6 is incubated after the completion of sintering small When, make its densification into porcelain, then it is cooled to normal temperature with stove.
5. Y according to claim 43+、Ga3+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, it is characterised in that： In the step (1), Ball-milling Time is 15-17 hours.
6. Y according to claim 43+、Ga3+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, it is characterised in that： In the step (2), sintered 4-5 hours at seed material obtained in step (1) is put into 1270-1280 DEG C.
7. Y3+, Ga3+ according to claim 4 are combined the preparation method of donor doping ZnO voltage-sensitive ceramics, and its feature exists In：In the step (4), the mass percent for adding poly-vinyl alcohol solution is 5%wt, and the ratio for adding poly-vinyl alcohol solution is 50g poly-vinyl alcohol solutions are added in every kilogram of mixture.
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